CN1104375A - Method for production of semi-conductor thermoelectric device and its material and apparatus thereof - Google Patents
Method for production of semi-conductor thermoelectric device and its material and apparatus thereof Download PDFInfo
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Abstract
A semiconductor thermo-electric device and its manufacturing method and equipment are provided, its characteristics are that, the thermo-electric arm adopts P type and N type semiconductor crystal balls. The crystal balls use bismuth, tellurium, selenium and bismuth, stibium, tellurium as raw material respectively, and are made by melting, dropping condensation and heat treating. The special equipment includes a quartz container with drop effuser, a condenser which is connected to the quartz container, a gas shield device and a vacuum system which are connected to the quartz container and the condenser respectively. Applying this method we can reduce the size of thermo-electric arm obviously, increase the unit refrigeration quantity of the thermo-electric device, reduce raw material loss and the production cost, and simplify the operation etc.
Description
The present invention relates to the manufacture method and the equipment of a kind of semi-conductor thermoelectric device and material thereof.
The direct refrigeration of paltie effect when thermoelectric device utilizes electric current to pass through semiconductor.Semiconductor heat electric refrigerator simple structure does not have the working medium circulation, does not have mechanical movement, and noiseless is pollution-free, small and light, is widely used on space technology, ocean development, electronics, medical treatment and many household electrical appliance, is particularly suitable for making Small Refrigerating Equipment.But thermoelectric device is for more powerful application, and as large refrigerator and air conditioner, it is promoted and also is subjected to the high and inefficient restriction of cost.Causing the high principal element of thermoelectric device cost is thermoelectric material and device fabrication complexity, and rate of finished products is low.
The structure of industrial so far typical heat electric device as shown in Figure 1, its elementary cell is a semiconductor thermocouple, a thermocouple arm P of galvanic couple p N-type semiconductor N material, another thermocouple arm N n N-type semiconductor N material, two thermocouple arm P, N connect with metal conductive strips B, C, after polarity adds direct voltage as shown, absorbing heat with the contact place of bonding jumper B, with the contact place heat release of bonding jumper C, A, D are the heat conductive insulating plate, by plate A cooling by heat absorption, emit by the heat that plate D will produce.Wherein key component is p type thermocouple arm P and n type thermocouple arm N, the efficient of their performance decision thermoelectric device work.Traditional thermoelectric arm all is the square section cylinder, and size is about 1～3mm, and the thermoelectric arm material mainly is that bismuth-tellurium is an alloy.The method of this thermoelectric material of manufacturing of present industrial practicality mainly is divided into two classes, and promptly crystal growth and powder sintering are made crystal ingot earlier, cut into the thermoelectric arm shape then, and there are a series of shortcomings in these two kinds of methods.
Crystal growth is that component raw material is mixed the back heat fused, becomes monocrystalline or polycrystalline ingot with normal freezing method or zone-melting process or Grown by CZ Method, as European patent EP 258361, and U.S. Pat 5108515 etc.This method might make the preferable material of thermoelectricity capability, and its technological process is: batching → fusion → crystal growth → heat treatment → orientation → section → stripping and slicing.Its defective is:＜1〉complex process, during operating cost;＜2〉during crystal growth because impurity segregation causes composition along the ingot skewness, the utilance of material is low;＜3〉crystal has tangible cleavage fissure, and is very fragile, breaks easily when cutting, assembling and use, because damage, cracking and fragmentation in the course of processing make rate of finished products very low, is difficult to use machinery during assembly device, needs manual careful operation.
For solving the problem of crystal growth, developed powder sintering.As day the disclosure specially permit flat 3-233980, flat 5-48125 and international monopoly WO 90-16086 etc., its technological process is: batching → fusion → quench solidification → fragmentation → screening → compacting → sintering → section → stripping and slicing.But also there is intrinsic shortcoming in powder sintering:＜1〉operation is many, requires sternly, and it is many to stain chance, and a day disclosure is speciallyyed permit flat 4-293276 and is adopted the fusion spray method of dripping to make fine powder to prevent to stain, but needs compacting sintering;＜2〉have a large amount of spaces and crystal boundary in the crystal ingot, thermoelectricity capability is worsened, carrier mobility descends, and resistivity increases, and Joule heat increases, and refrigeratory capacity reduces;＜3〉doping is difficult to control, adds a certain amount of impurity and can not necessarily obtain required carrier concentration, therefore with same prescription and process conditions, is difficult to repeat to obtain satisfied material behavior.
What these two kinds of methods made all is crystal ingot, make thermoelectric arm and also crystal ingot must be cut into fritter.From the thermoelectric device technological principle as can be known, for a certain amount of material, obtain bigger specific refrigerating effect, the thermoelectric arm size should be as far as possible little, but make the restriction that little thermoelectric arm is subjected to cutting loss, the cube that present technical feasible lower limit is the 1mm length of side, adopt present cutting technique, if the cube of the cutting 0.5mm length of side, only the loss of cutter seam just reaches 80%, and owing to the cutting affected layer on surface, the availability of material is lower again, technical infeasible, therefore its refrigerating capacity of thermoelectric device with present technology manufacturing is restricted.
In a word, the method operation of existing manufacturing thermoelectric material is many, and loss is big, the quality control difficulty, and the specific refrigerating effect of device is little, and the cost height is unfavorable for the application of more high-power refrigeration.
The object of the invention is to improve the structure of thermoelectric device, proposes the manufacture method and the equipment of relevant semi-conducting material, thereby simplifies technology, reduces loss, improves performance and reduce cost.Specifically, propose a kind of thermoelectric device of new construction, semiconductor thermoelectric arm wherein is spherical, and promptly p N-type semiconductor N geode and n N-type semiconductor N geode make thermoelectric device have stronger refrigerating capacity, higher mechanical strength and superior manufacturability; Adopting the molten drop method to make bismuth-tellurium continuously is the alloy geode, and its process is batching → fusion → drop balling-up → heat treatment, the geode diameter unanimity of making, and surface-brightening is formed evenly, and compact structure has higher figure of merit; The special equipment of semiconductor geode is produced in design, and by disposing suitable drop jet pipe, coolant and protective gas device realize that semiconductor bismuth-tellurium is the serialization production of alloy geode, have production efficiency height, low, the rate of finished products advantages of higher of cost.
For realizing that purpose of the present invention adopts following technical measures:
1. square column type semiconductor thermoelectric arm adopts the semiconductor geode to replace in the conventional thermoelectric device, and this new structure thermoelectric device has the refrigeration performance more excellent than conventional device, has higher intensity simultaneously, better manufacturability;
2. adopting the molten drop method to make semiconductor bismuth-tellurium continuously is the alloy geode, by selecting of melt temperature, spout internal diameter, injection rate, vibration frequency and coolant, control geode diameter and internal crystal structure thereof, the semiconductor die bulb diameter unanimity of making, surface-brightening, form evenly compact structure;
3. design a kind of equipment of making the semiconductor geode that is exclusively used in, suitable drop jet pipe, cooling fluid and the gas system of configuration in this equipment realized stable continuous manufacturing geode.
Essence of the present invention is to change the semiconductor column piece as thermoelectric arm in the thermoelectric device into geode, and the method and apparatus of making this geode is provided simultaneously.
According to the thermoelectric device principle, the refrigeratory capacity of device under maximum freezing capacity state
Q
0＝ (α
2M(Th-Tc)(MTc-Th))/(R(M-1)
2(M+1)) （1）
Wherein,
M＝[1+Z（Th+Tc）/2]
1/2
In the formula, α-thermoelectric power, Th-hot junction temperature, Tc-cold junction point temperature,
R-thermocouple resistance, the figure of merit of Z-material.
In order to obtain to try one's best big refrigeratory capacity under greater efficiency, the thermocouple resistance R should be as far as possible little as can be known by (1) formula.For the thermoelectric material of unit quantity, the all-in resistance of square thermoelectric arm is:
R＝ρ＊L
2
Wherein, the resistivity of ρ-material, the length of side of the square thermoelectric arm of L-.
Therefore, reduce length of side L, refrigeratory capacity Q
OIncrease with quadratic relationship.Yet square thermoelectric arm length of side L reduces to be subjected to the restriction of technical conditions, and by present cutting technique level, during the cube of the cutting 1mm length of side, only the loss of cutter seam just reaches 60%, and this is the minimum dimension that present thermoelectric device is produced.If the cube of the cutting 0.5mm length of side, the loss of cutter seam will be above 80%, and the surface damage layer thickness that cutting at this moment causes is approaching with component size, so impracticable.
For spherical thermoelectric arm, the resistance of Board Lot thermoelectric material is:
R＝0.548ρ＊d
2
Wherein d is the geode diameter.Make the restriction that geode is not cut, diameter can be very little, so resistance is very little, can obtain big refrigeratory capacity under higher freezing capacity.The thermoelectric material of equivalent, the spherical arm device refrigeratory capacity of 0.5mm diameter are 4～6 times of the square arm device of the 1mm length of side.
The key of success of the present invention be make that thermoelectric property is good, compact structure and the uniform bismuth-tellurium of diameter is the geode of alloy.It is geode that the present invention is used for after with the drop technological improvement making n type and the p type bismuth-tellurium of forming accurately control continuously.
By required composition preparation, heating and melting mixes, and passes through lip jet with feed metal.The theory of become dripping according to jet [N.R.Linblad and J.M.Scheider, J.Sci. Instr.42,6,35(1965)] obtains single size drop optimum flow rate and is:
Vm＝f＊ds＊π（2+6.We
1/2/Re）
1/2
This moment, the gained liquid-drop diameter was:
d＝ds[1.5π（2+6We
1/2/Re）
1/2]
1/3
F-vibration frequency in the formula, the We-Weber number, the Re-Reynolds number,
The ds-jet diameter, dD has relation with capillary diameter:
ds＝β＊dD
Factor beta=0.866 wherein
For metal We
1/2/ Re=0.001～0.004＜＜1 can obtain:
Optimum flow rate Vm=4.4ds*f (2)
Liquid-drop diameter d=1.88ds=1.63dD (3)
Therefore optimum flow rate and vibration frequency are chosen according to (2) formula, and liquid-drop diameter is determined according to (3) formula by the spout internal diameter.
The geode that is applicable to thermoelectric device must have good profile, internal structure and thermoelectric property, and the cooled and solidified process of molten drop is crucial.Bismuth-tellurium is that the characteristics of alloy are that melting heat is big, and conductive coefficient is little, therefore for big geode, gas cooled is inapplicable, it is the rerum natura and the rapid solidification thereof of alloy that the present invention has studied bismuth-tellurium, and for the cooling that forces of big geode employing cooling fluid, drop is rapidly solidificated into geode.Regulate effluxvelocity and cooling condition, make the thermoelectric geode of diameter unanimity, the inner uniform crystal particles of while geode, dense structure, not having bismuth-tellurium is the cleavage phenomenon of crystal, geode intensity height, and have good thermoelectricity capability.
Description of drawings:
Fig. 1 is traditional thermoelectric device structural representation.
Fig. 2 is a thermoelectric device structural representation of the present invention.
Fig. 3 is for making the device structure schematic diagram that the semiconductor geode is used.
Fig. 4 is spherical arm thermoelectric device performance plot.
Fig. 5 is the thermoelectric material metallograph, and wherein a) powder sintered thermo electric material metallograph b) is the metallograph of semiconductor geode of the present invention.
Below in conjunction with description of drawings, be described in detail particular content of the present invention.
Thermo-electric device structure of the present invention as shown in Figure 2, the elementary cell of its structure is semiconductor thermocouple, a galvanic couple arm P p-type semi-conducting material manufacturing, another galvanic couple arm N N-shaped semi-conducting material manufacturing, galvanic couple arm P, connect by metal conductive strips B between the N, many to connecting by metal conductive strips C between the galvanic couple, all galvanic couples equidistantly are arranged in heat conductive insulating plate A, between the D, galvanic couple arm P, N and metal conductive strips B, C and metal conductive strips B, C and heat conductive insulating plate A, respectively welding between the D, it is characterized in that: p-type semiconductor galvanic arm P adopts p-type semiconductor geode, and N-shaped semiconductor galvanic arm N adopts N-shaped semiconductor geode. The diameter of geode can be for 0.1 to 3mm, also can be littler than 0.1mm. The contact-making surface of geode and bus B, C is sphere, and subtended angle 2 ψ of contact-making surface can choose between 90～120 °, generally take 100～110 ° as good.
Wherein the N-shaped semiconductor N is respectively the identical N-shaped of diameter with p-type semiconductor P and p-type bismuth-tellurium is the alloy geode, heat conductive insulating plate A and D adopt has better thermal conductivity and the ceramic sheet of electric insulation or the aluminium sheet that the process anodized forms surface insulation layer, its inboard bar shaped ambrose alloy metal level that forms, be bus B, C, geode and bus B, C welding, design by figure makes many to P-N semiconductor thermocouple serial or parallel connection, and the cold that produces and heat are spread out of by heat conductive insulating plate A and D respectively.
With computer spherical thermoelectric arm device is simulated, and done contrast with traditional square thermoelectric arm device, condition is that the material of two kinds of shapes has identical weight and the thermoelectric property parameter is identical, comprises thermoelectric power, resistivity, thermal conductivity factor and contact resistivity. The result shows, spherical thermoelectric arm device is when subtended angle 2 ψ of contact-making surface=108 °, and the square thermoelectric arm of the resistance ratio of geode is little about 16%, and therefore, when efficient (COP) was the highest, spherical thermoelectric arm device refrigeratory capacity was about 1.3 times of square thermoelectric arm device.
According to the thermo-electric device principle, littler structure is conducive to increase the unit are refrigeratory capacity, and difficulty of the 1mm length of side is accomplished in the restriction that cylindrical material is cut, and the geode diameter is not difficult to accomplish below the 0.5mm. According to calculating, under identical COP condition, adopt the equivalent material, spherical thermoelectric arm device specific refrigerating effect can reach more than 4 times of square thermoelectric arm device, and therefore, the geode structure is obviously favourable aspect the increase refrigerating capacity.
A kind of manufacture method of semi-conductor thermoelectric material, the base stock of p-type galvanic couple arm P is bismuth, tellurium and antimony, and the base stock of N-shaped galvanic couple arm N is bismuth, tellurium and selenium, through being melt into crystalline substance, it is characterized in that: with raw material by the proportioning melting, mixed, become to drip, solidify, form geode; Wherein material melting, the protective gas that becomes to drip, solidifies are high-purity inert gas or nitrogen; The raw material initial fusion temperature is above 30～50 ℃ of alloy melting point, and the temperature by drop jet pipe jet is above 5～20 ℃ of alloy graining point, and coolant temperature is selected maintenance constant temperature between room temperature to 60 ℃; Effluxvelocity 0.5～2 meter per second applies vibration 50～1000Hz to jet.
Geode can be in heat treatment 0.5～1 hour in high purity inert gas or blanket of nitrogen between 300～450 ℃.
The manufacturing process flow of thermoelectric material comprises batching, melting, and molten drop balling-up and heat treatment is characterized in that spraying to drip to solidify together after raw materials melt mixes finishing, and directly form the geode of consistent size. Concrete steps are take the bismuth of purity 5N, tellurium, selenium as raw material, pack into by suitable proportioning In the quartz container, be evacuated to below the 2Pa, airtight above 30～50 ℃ of the alloy melting point that is heated to, be incubated 1 hour, apply simultaneously the 8Hz vibration and stir melt, cool to above 5～20 ℃ of freezing point, pass into the protective gas of purity 5N, liquation sprays with 0.5～2 meter per second speed by the drop jet pipe, applies 50～1000Hz vibration, and molten drop falls into cooler and forms geode; Take out at last geode, with organic solvent deoil after in protective atmosphere 300～450 ℃ annealing 0.5～1 hour, make N-shaped semiconductor geode; Take the bismuth of purity 5N, antimony, tellurium as raw material, pack in the quartz container by proportioning, be evacuated to below the 2Pa, airtightly be heated to 30～50 ℃, be incubated 1 hour, apply simultaneously the 8Hz vibration, cool to 5～20 ℃ and pass into the protective gas that purity is 5N, liquation sprays with 0.5～2 meter per second speed by the drop jet pipe, apply 50～1000Hz vibration, molten drop falls into the cooler cooling and forms geode, after geode is deoiled with organic solvent, in protective atmosphere, annealed 0.5～1 hour for 300～450 ℃, make p-type semiconductor geode; When making p-type semiconductor geode, proportioning components can be at 15～17wt% Bi, 53～59wt% Te, 32～24wt% Sb, between select, also can add in addition 1～5wt% selenium Se; When making N-shaped semiconductor geode, its proportioning components can be at 48～54wt% Bi, regulates in the 47～48wt% Te, 5～3wt% Se, also can add in addition 1～5% iodine I or antimony Sb, and alloy composition of the present invention is not restricted, and goes for multiple alloy composition; Protective atmosphere is inert gas or nitrogen.
A kind of special equipment of implementing said method; structural representation as shown in Figure 3; it is characterized in that: by quartz container 1; drop jet pipe 2; heating furnace 3; temperature-controlled power 4; vibrator 5; audio-frequency generator 6; cooler 7; oil-sealed rotary pump 8; high-purity gas cylinder 9; pressure-reducing valve 10; control valve 11; flowmeter 12; difference gauge G valve; pipeline forms; wherein drop jet pipe 2 is arranged on the bottom of quartz container 1; cooler 7 is connected on the below of quartz container 1; oil-sealed rotary pump 8 is by valve K4; K3; K2 is connected with quartz container 1; pass through K4; K5 is connected with cooler 7; high-purity gas cylinder 9; pressure-reducing valve 10; control valve 11; flowmeter 12; valve K1 serial connection; be connected with quartz container 1 by K2; by valve K3; K5 is connected with cooler 7; are connected with cooler with quartz container 1 respectively and are connected in difference gauge G two ends; placed the top of quartz container 1 by the vibrator 5 of audio-frequency generator 6 controls; heating furnace 3 is by temperature-controlled power 4 power supplies; cooler 7 is provided with by filter 13; the EGR that pump 14 and heat exchanger 15 consist of; emptying valve K6 and discharge valve K7; place the raw material of quartz container 1 to melt in a vacuum; liquation penetrates from drop jet pipe 2 in high-purity protection gas, and jet velocity and vibration frequency are according to difference gauge G reading Regulated by control valve 11, drop enters cooler 7 cooled and solidified and becomes the semiconductor geode.
Used cooling medium is mineral oil or silicone oil in the cooler 7, and the internal diameter of drop jet pipe 2 is 0.1～2mm.
With prior art relatively, the present invention has following outstanding advantage:
1. the spherical thermoelectric arm of thermo-electric device can be made 0.5mm even smaller szie, adopts the material of same performance index, and its performance factor can reach conventional square thermoelectric arm device more than 4 times.
2. semiconductor geode manufacturing process is simple, and geode size uniform, the circularity made are good, surface-brightening, and inner pore-free, free from flaw, internal stress is little, and the mechanical strength height is easy to assembling, and the device of making is more durable.
3. geode forms by the high speed condensation, do not form fractional condensation, so component is even, and composition can accurately be controlled, and crystal grain is thin and even simultaneously, the crystal structure densification, so electrical conductivity is higher, and thermal conductivity reduces, and the result increases the figure of merit of material.
4. get rid of crystal growth, the sintering compacting of trouble, need not cutting, not only time saving and energy saving, reduce and stain, and greatly reduced spillage of material, common process material overall utilization is lower than 8%, adopts geode process materials utilization rate to be higher than 90%.
5. make the geode that can be used for assembling thermo-electric device from raw material, flow process is finished in a device continuously, and operation is few, and energy consumption is low, low equipment investment, and the device assembling is easier to, and is beneficial to Make broad area device, be beneficial to the mechanization batch production.
6. because advantage 1 and 4, for producing identical refrigerating capacity, utilize the required raw material consumptions such as valuable bismuth, tellurium, selenium and antimony of ball-type thermoelectric arm device of the present invention less than 1/50th of the square thermoelectric arm device of routine, add energy consumption and operation labour's saving, greatly reduce the cost of thermoelectric material.
In a word, adopt thermo-electric device structure of the present invention and geode manufacturing process and equipment can realize thermo-electric device production high-quality, low consumption, the cost of decrease thermoelectric cooling needing to be particularly suitable for the greatly application scenario of refrigerating capacity.
Embodiment 1:
A kind of structure thermoelectric device as shown in Figure 2, adopt each 16 of p type and n N-type semiconductor N geodes, constitute 16 pairs of thermocouples, the geode diameter is 0.5mm, p N-type semiconductor N geode composition is 15.71wt%Bi, 26.05wt%Sb, 58.24wt%Te, n N-type semiconductor N geode composition is 53.16wt%Bi, 43.82wt%Te, 3.02wt%Se, heat conductive insulating plate A, D adopts alumina ceramic plate, plate is provided with bus B, C, p type and n N-type semiconductor N geode equidistant placement, integrally welded by bus B and C series connection, it is 108 ° that the knot of geode and bus touches the face subtended angle, DC power supply E is 1.0V, and its characteristic is shown in Fig. 4.When refrigerating efficiency is 0.88, refrigeration 0.6W, and thermoelectric arm is when being the 1mm square, refrigerating efficiency is 0.87, refrigeration 0.14W.Use the equivalent material, spherical thermoelectric arm device refrigeratory capacity is 4.3 times of square thermoelectric arm device.
Embodiment 2:
By 15.7,58.2, the quartz container 1 of packing into after the 26.1wt% proportioning is evacuated to 2Pa with oil-sealed rotary pump, and is airtight, is heated to 630 ℃, is incubated 1 hour with 5N high purity bismuth, tellurium and antimony, applies the 8Hz vibration simultaneously.Cool to 615 ℃ then, feed high pure nitrogen, make liquation pass through the speed ejection of the capillary of internal diameter 0.9mm with 0.6 meter per second, apply the vibration of 200Hz, jet is dispersed into symmetrical liquid drop, falls into cold oil behind nitrogen, and oil is in room temperature, and molten drop is frozen into geode.Making the geode diameter is 1.55mm, surface-brightening such as mirror, and geode is taken out the back and is cleaned the back 380 ℃ of annealing half an hour in high purity nitrogen of deoiling with organic solvent, and its composition analysis data are listed in table 1, and geode is a p type conduction, and the thermoelectricity capability data are listed in table 2.
By 53.2,43.8, the quartz container 1 of packing into after the 3.0wt% proportioning is evacuated to 2Pa with oil-sealed rotary pump, and is airtight, is heated to 620 ℃, is incubated 1 hour with 5N high purity bismuth, tellurium and selenium, applies the 8Hz vibration simultaneously.Cool to 605 ℃ then, feed high pure nitrogen, make liquation pass through the speed ejection of the capillary of internal diameter 0.9mm with 0.6 meter per second, apply the vibration of 200Hz, jet is dispersed into symmetrical liquid drop, falls into cold oil behind nitrogen, and oil is in room temperature, and molten drop is frozen into geode.Making the geode diameter is 1.55mm, surface-brightening such as mirror, and geode is taken out the back and is cleaned the back 380 ℃ of annealing half an hour in high purity nitrogen of deoiling with organic solvent, and its composition analysis data are listed in table 1, and geode is a n type conduction, and the thermoelectricity capability data are listed in table 2.
Fig. 5 is the metallograph of thermoelectric material.A) be the thermoelectric material metallograph of powder sintered manufactured wherein; B) be p type of the present invention and n N-type semiconductor N geode metallograph.As seen thermoelectric material of the present invention is formed more even, and structure is finer and close.
Embodiment 3:
The production equipment of the semiconductor geode that a kind of thermoelectric device is used, adopt structure as shown in Figure 3, quartz container 1 volume is 100 milliliters, drop jet pipe 2 adopts quartz capillary, internal diameter is 0.90mm, cooler 7 upper ends and quartz container 1 sealing-in highly are 120cm, and wherein the cooling fluid height is 80cm.By the proportioning components of setting raw material are added in the quartz container 1, gas system is made of high-purity gas cylinder 9, pressure-reducing valve 10, adjuster valve 11, flowmeter 12, difference gauge G, valve K1～K7 and connecting tube, be connected with cooler 7 with quartz container 1 respectively, press the method for embodiment 2, make the geode of p type or n N-type semiconductor N.
Claims (6)
1, a kind of semi-conductor thermoelectric device, the elementary cell of its structure is a semiconductor thermocouple, a galvanic couple arm [P] p N-type semiconductor N material, another galvanic couple arm [N] n N-type semiconductor N material, galvanic couple arm [P], connect by metal conductive strips [B] between [N], many to connecting by metal conductive strips [C] between the galvanic couple, all galvanic couples equidistantly are arranged in heat conductive insulating plate [A], between [D], galvanic couple arm [P], [N] and metal conductive strips [B], [C] and metal conductive strips [B], [C] and heat conductive insulating plate [A], welding respectively between [D], it is characterized in that: p N-type semiconductor N galvanic couple arm [P] adopts p N-type semiconductor N geode, and n N-type semiconductor N galvanic couple arm [N] adopts n N-type semiconductor N geode.
2, according to the semi-conductor thermoelectric device of claim 1, it is characterized in that: the diameter of described semiconductor geode [P], [N] is 0.1～3.0mm; The subtended angle of geode and metal conductive strips [B], [C] contact-making surface is 90～120 °.
3, a kind of manufacture method of semi-conductor thermoelectric material, the base stock of p type galvanic couple arm [P] is bismuth, tellurium and antimony, and the base stock of n type galvanic couple arm [N] is bismuth, tellurium and selenium, through being melt into crystalline substance, it is characterized in that: with raw material by the proportioning fusion, mixed, become to drip, solidify, form geode; Wherein material fusion, the protective gas that becomes to drip, solidifies are high-purity inert gas or nitrogen; The raw material initial fusion temperature is above 30～50 ℃ an of alloy melting point, and the temperature by drop jet pipe jet is above 5～20 ℃ of an alloy graining point, and coolant temperature is selected maintenance constant temperature between room temperature to 60 ℃; Effluxvelocity 0.5～2 meter per second applies vibration 50～1000Hz to jet.
4, according to the manufacture method of the semi-conductor thermoelectric material of claim 3, described geode can be in heat treatment 0.5～1 hour in high purity inert gas or blanket of nitrogen between 300～450 ℃.
5; a kind of equipment of implementing the described method of claim 3; it is characterized in that: by quartz container [1]; drop jet pipe [2]; heating furnace [3]; temperature-controlled power [4]; vibrator [5]; audio-frequency generator [6]; cooler [7]; oil-sealed rotary pump [8]; high-purity gas cylinder [9]; pressure-reducing valve [10]; adjuster valve [11]; flowmeter [12]; difference gauge [G]; valve; pipeline is formed; wherein drop jet pipe [2] is arranged on the bottom of quartz container [1]; cooler [7] is connected on the below of quartz container [1]; oil-sealed rotary pump [8] is by valve K4; K3; K2 is connected with quartz container [1]; pass through K4; K5 is connected with cooler [7]; high-purity gas cylinder [9]; pressure-reducing valve [10]; adjuster valve [11]; flowmeter [12]; valve K1 serial connection; be connected with quartz container [1] by K2; by valve K3; K5 is connected with cooler [7]; difference gauge [G] two ends are connected with cooler [7] with quartz container [1] respectively; place the top of quartz container [1] by the vibrator [5] of audio-frequency generator [6] control; heating furnace [3] is powered by temperature-controlled power [4]; cooler [7] is provided with by filter [13]; the circulating device that pump [14] and heat exchanger [15] constitute; emptying valve K6 and discharging valve K7; place the raw material of quartz container [1] to melt in a vacuum; liquation penetrates from drop jet pipe [2] in high-purity protection gas; jet velocity and vibration frequency are regulated by adjuster valve [11] according to difference gauge [G] reading, and drop enters cooler [7] cooled and solidified and becomes the semiconductor geode.
6, according to the equipment of claim 5, used coolant is mineral oil or silicone oil in the cooler [7], and the internal diameter of drop jet pipe [2] is 0.1～2mm.
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|---|---|---|---|
| CN94112273A CN1034199C (en) | 1994-08-20 | 1994-08-20 | Method for production of semi-conductor thermoelectric device and its material and apparatus thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100411212C (en) * | 2002-12-06 | 2008-08-13 | 株式会社明电舍 | Thermoelectric effect apparatus, energy direct conversion system, and energy conversion system |
| WO2014206164A1 (en) * | 2013-06-25 | 2014-12-31 | 苏州伟源新材料科技有限公司 | Method for manufacturing n-type semiconductor element for refrigeration or heating device |
| CN106024732A (en) * | 2016-05-31 | 2016-10-12 | 科大国盾量子技术股份有限公司 | Device for temperature control and manufacturing method of device |
| CN106546034A (en) * | 2016-11-30 | 2017-03-29 | 武汉工程大学 | A kind of calorstat heated based on semiconductor refrigerating |
| CN110282975A (en) * | 2019-07-08 | 2019-09-27 | 先导薄膜材料（广东）有限公司 | A kind of Germanium selenide target and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL85389A (en) * | 1988-02-10 | 1991-06-10 | Israel Atomic Energy Comm | Thermoelectric devices |
-
1994
- 1994-08-20 CN CN94112273A patent/CN1034199C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100411212C (en) * | 2002-12-06 | 2008-08-13 | 株式会社明电舍 | Thermoelectric effect apparatus, energy direct conversion system, and energy conversion system |
| WO2014206164A1 (en) * | 2013-06-25 | 2014-12-31 | 苏州伟源新材料科技有限公司 | Method for manufacturing n-type semiconductor element for refrigeration or heating device |
| AU2014301910B2 (en) * | 2013-06-25 | 2016-11-17 | Zhiming Chen | Method for manufacturing N-type semiconductor element for refrigeration or heating device |
| US10100437B2 (en) | 2013-06-25 | 2018-10-16 | Zhiming Chen | Method for manufacturing N-type semiconductor element for cooling or heating device |
| CN106024732A (en) * | 2016-05-31 | 2016-10-12 | 科大国盾量子技术股份有限公司 | Device for temperature control and manufacturing method of device |
| CN106546034A (en) * | 2016-11-30 | 2017-03-29 | 武汉工程大学 | A kind of calorstat heated based on semiconductor refrigerating |
| CN106546034B (en) * | 2016-11-30 | 2019-05-03 | 武汉工程大学 | A kind of insulating box based on semiconductor refrigerating heating |
| CN110282975A (en) * | 2019-07-08 | 2019-09-27 | 先导薄膜材料（广东）有限公司 | A kind of Germanium selenide target and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1034199C (en) | 1997-03-05 |
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